Vat dyestuff preparations of improved vatting properties



United States Patent c1. 8-34 I 10 Claims ABSTRACT OF THE "DISCLOSURE Dyestufif preparations containing a vat dye, sodium dithionite as reducing agent and, as an assistant, amino-- anthraquinone sulfonic acid,- aminoanthraquinone s'ulfonamide, aminoanthraquinone sulfonic acid ester or a salt of aminoanthraquinone sulfonic acid and their use in the dyeing of cellulosic materials.

,The present invention relates todyestuif preparations containing a-new type of dye and printin'gassistant and products dyed and printed therefrom. y

Quite a number of processes are already known that allow an improvement of the vatting property of vat dyestufi preparations. However, the majority of these processes'can be employed only for the printing with vat dyestuffs, w hereas they do not produce any improvement in' the dyeing; I British Pats. 349,955 and 378,553teach that hydroxyanthraquinones a reduci g catalys s imprcvethe va in property of vat and sulfur dyestuffs in printing. U.S.-'- Pat. 2,371,102 recommends for the dyeing and printing the employment of N,N'-d ianthraquinonyl furnaric acid diamides asassistants in order to improve the vatting properties. British Pat. 975,967 teaches the utilization of cobalt (II) salts of the Z-hydroxyand 2,6-dihydroxyanthraquinone as a vatting accelerator. Moreover, it is known from US. Pats. 2,371,101 and 2,405,151 to use for said purpose arylamine salts of anthraquinone mono and disulfonic acids as welllas anthraquinonyl sulfonamides.

vHowever, all the vatting accelerators. as mentioned above show, particularly in dyeing, only slight effects so that their employment is of no noteworthy significance in practice. I v

Modern dyeing methods, however, require a very rapidvattingof the vat dyestufls employed. In order to meet these requirements, suitable dyestuif preparations had. to be made, so far, partly with a great expenditure that lies, for example, in wearisome and lengthy grinding operations on high quality grinding aggregates or in troublesome reprecipitation measures. Moreover, quite a number of valuable vat dyestuffs cannot be brought into an appropriate form and, therefore, cannot be employed for said purpose at all.

We, now have found that the vatting property of vat dyestuffs can be improved to an extent that is far superior to prior art by vatting the dyestuffs after the addition of 3,512,917 Patented May 19, 1970 small amounts of aminoanthraquinone sulfonic acids or functional derivatives thereof, which may contain further substituents. Generally, an addition of 0.001 to 5% by weight, preferably 0.01 to 2% by weight, of the auxiliary agent under this invention, related to the weight of the dyestutf employed, is sufficient.

Aminoanthraquinone sulphonic acids andderivatives thereof, which may contain further substituents, suited for the process under this invention are, for example, 0 monoand disulfonic acids of monoand polyaminoanthraquinones, 1 amino 4-bromanthraquinone-Z-sulfonic acid and its arylamino derivatives, aminohydroxyanthraquinone sulfonic acids, alkali salts of the amino- ,anthraquinone sulfonic acids, organic amino salts of the aminoanthraquinone sulfonic acids, aminoanthraquinone sulfonamides deriving from primary and secondary aliphatic and aromatic amines, aminoanthraquinone sulfonic acid esters and the like. The 1-amino-anthraquinone-2-, -4- or -5-sulfonic acids or their derivatives and substitution products have proved to have a particularly valuable elfect.

The elfectiveness of aminoanthraquinone sulfonic acids 7 containing the amino group and the sulfo group in the same nucleus, is not increased by the introduction of a further sulfonic acid group but is enhanced by the intro duction of a further hydroxyl or arylamino group or a halogen atom into the same nucleus or of an amino group into the non-substituted nucleus as is evident, for example, from the case of the '1,5-diaminoanthraquinone-2- sulfonic acid.

The aminoanthraquinone sulfonic acids and the like may be added either to the dye liquor or the printing paste; however, the auxiliary agents utilizable under the present invention may previously be incorporated into the dyeformulations used for the preparation of the dye liquors or printing pastes. The vatting accelerators under this invention are particularly valuable in that they produce their excellent effect in the dyeing and printing operations as well.

The dyecompositions according to the present invention are suited for dyeingand printing any sort of cellulosic materials such as cotton, rayon, staple fiberj'mixed EXAMPLE 1 Comparative dyeing tests'directed to examine the vatting acceleration effected by various anthraquinone derivatives in a long vatting bath:

.Each time 2 dye liquors are prepared with 2%. Indanthren-Brilliant Pink RS (Colour Index No. 73360) together with 10 cc. per liter sodium hydroxide solution of 38 B.'and 4 g. per liter sodiumdithionite, whereby one of the "dye liquors is admixed with 0.01 g. per liter of the vatting accelerator;

After the introduction of cotton yarn into the bath, (liquor ratio 1:20), at 20, the temperature of the liquor is raised to 50 within 5 minutes and kept at this temperature for 10 minutes. The dyeings are subsequently oxidized, rinsed, and so'apedin the usual manner;

The comparison of the color yields between the dyeings 1-aminoanthraquinone-2-sulfonic acid-N-methobtained with a vatting accelerator and those obtai e yl-N-phenylamide without said accelerator is evaluated as follows: N,N'-di-a-anthraquinonyl furnaric acid diamide 1 equal coloring strength in both cases '1 "7'". ""7"" slight improvement in the case where the vatting acg i anthraqumonyl'fuman9 acld dlam' celerator is added. "'f'".""'?" 2 good improvement 1n the case where the vatting ac- Cobalt (In complex of the anthraflavlmc acld celerator is added Cobalt (II; complex of the Z-hydroxyanthraver ood im rovement in the case where the vatqumone. ""1 is gdded Anthraflavinic acid (accordlng to Brltish Patsuperior improvement in the case where the vatems 349955 and 378,553

ting is addedarena r: ra-aaaaaa 1 1 The following table enumerates the anthraquinone derivatives examined:

EXAMPLE 2 1-arrunoanthraqu1none-2-sulfon1c acid I 1-aminoanthraquinone-4-sulf0nic acid Examination of the vattingacceleration of various vat 1-aminoanthraquinone-5-sulfonic acid dyestuffs by means of 1-am1noanthtaqumone-Z-sulfomc 1-aminoanthraquinone--sulfonic acid acid (A) or 1,5-d1ammoanthraqumone-Z-sulfonic acid 1-am1noanthraqu1none-7-su1fon1c acid +1+ (B):

Vettin accelerator in percent by weight related Percentage Color to the decrease in Index weight of vatting Dyestufi No. Vetting the dyestnfi time Indanthren-Scerlet GK. 59310 Long bath at 50.. 1% B 4a Indanthren -Yel1ow F2 Concentrated 1% B 50 GO. vetting at 50.

Do 59310 --do 1% Indanthren-Ruby RS-.." 70320 Long bath at 60 Do 73020 do 1 10 Indanthren-Orange 4R.- 59710 Corrttairg'aatego 32 V Indanthren-Blue RS 69800 Long bath at 60 43 n 69800 .do 1 71 73360 Concentrated 58 vatting at 75.

Vetting time inminutes:

Not vatt able. 48 22 12 l 0.1. vat yellow.

Z-aminoanthraquinone-6-sulfonic acid Z-aminoanthraquinone-7-sulfonic acid ,+a+ l-aminoanthraquinone-2,S-disulfonic acid 1-aminoanthraquinone-2,7-disulfonic acid 1-aminoanthraquinone-4,6-disulfonic acid 2-aminoanthraquinone-3,6-disulfonic acid 2-aminoanthraquinone-3,7-disulfonic acid 1+i+ 1,S-diaminoanthraquinone-Z-sulfonic acid l-amino 4 bromoanthraquinone 2 sulfonic 1-aminoanthraquinone-Z-sulfonic acid-phenyl amide Vatting was effected in the manner as is customary for Indanthren-dyestufls. As regards the concentrated vatting, operation was done according to the directions of the Indanthren dyeing manual. Vatting in the long bath was run with 1 g./1. of the dyestuif each time.

The vatting procedure was followed with the aid of a spectrophotometer by measuring the transparency of the vat increasing commensurately witih the progressive vatting. The percentage decrease in the time necessary to effect vatting was determined from the relation to a blank test, i.e., a. vat to which no vatting accelerator is added.

It will be understood that this invention is susceptible to further modification and, accordingly, it is desired to comprehend such modification within this invention as may fall within the scope of the appended claims.

We claim:

'1. A'dye-compos'ition comprising a vat dye, sodium dithionite as the reducing agent and, as an assistant, an aminoanthraquinone sulfonic acid, an aminoanthraquinone sulfonamide; an aminoanthraquinone sulfonic acid ester or a salt'of an aminoanthraquinone sulfonic acid, said composition containing 0.001 to 5% by weight of said assistant based on the weight of said vat dye.

2. The dye composition of claim 1 containing 0.01 to 2% by weight of said assistant based on the weight of said vat dye.

3. The dye composition of claim 1 wherein said assistant is l-aminoanthraquinone sulfonic acid.

4. The dye composition of claim 1 wherein said assistant is Z-aminoanthraquinone sulfonic acid.

5. The dye composition of claim 1 wherein said assistant is 4-aminoanthraquinone sulfonic acid.

6. The dye composition of claim 1 wherein said assistant is S-aminoanthraquinone sulfonic acid.

7. The dye composition of claim 1 wherein said assistant is 1-arninoanthraquinone-Z-sulfonamide.

3. A dye liquor containing a dye composition of claim 1.

9. A printing paste containing a dye composition of 15 claim 1.

10. An article of manufacture comprising a cellulosic fabric dyed or printed with a dye composition of claim 1.

References Cited UNITED STATES PATENTS 3,118,724 1/1964 Goerrig et al. 8-34 3,273,955 9/1966 Goerrig et a1. 8-34 FOREIGN PATENTS 787,343 12/ 1957 Great Britain.

NORMAN G. TORCHIN, Primary Examiner J. E. CALLAGHAN, Assistant Examiner 

